CN1743954A - Etch-resisting pattern formation method, fine pattern formed thereby and method for making liquid crystal displaying component - Google Patents
Etch-resisting pattern formation method, fine pattern formed thereby and method for making liquid crystal displaying component Download PDFInfo
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- CN1743954A CN1743954A CNA2005100845386A CN200510084538A CN1743954A CN 1743954 A CN1743954 A CN 1743954A CN A2005100845386 A CNA2005100845386 A CN A2005100845386A CN 200510084538 A CN200510084538 A CN 200510084538A CN 1743954 A CN1743954 A CN 1743954A
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- corrosion
- pattern
- resisting pattern
- stepped
- formation method
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- MOZWGCRWGKSWAJ-UHFFFAOYSA-N phenol;1,2-xylene Chemical class OC1=CC=CC=C1.CC1=CC=CC=C1C MOZWGCRWGKSWAJ-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Thin Film Transistor (AREA)
Abstract
The method for forming a resist pattern includes the steps of (A) forming a photoresist coating film on a substrate 10 and (B) patterning the photoresist film into a step-like resist pattern R having a thick portion r1 and a thin portion r2 by a photolithographic process including selective exposure, wherein the photoresist coating film is formed by using a positive photoresist composition containing (a) an alkali-soluble novolac resin having over 8,000 mass average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography, (b) a naphthoquinonediazide group-containing compound and (d) an organic solvent.
Description
Technical field
The present invention relates to the formation method of corrosion-resisting pattern, the formation method of fine pattern of using this method and the manufacture method of liquid crystal indicator.In addition, the eurymeric resist composition that also relates to the formation method of the formation method that is suitable for this corrosion-resisting pattern and fine pattern.
Background technology
For example, in the manufacturing of the TFT of liquid crystal display cells (thin film transistor (TFT)) array base palte, adopt the photo-mask process that has used the photoresist tunicle usually.
Fig. 2～Figure 15 represents to make the example of operation of α-Si (amorphous silicon) shape tft array substrate of structure shown in Figure 16.In this embodiment, at first as shown in Figure 2, on glass substrate 1, form gate electrode layer 2 '.
Then, go up formation photoresist tunicle at gate electrode layer 2 ', by comprising this photoresist tunicle is carried out the photoetching process of the operation of selectivity exposure, on this photoresist tunicle, form pattern, form corrosion-resisting pattern R1 (the 1st photo-mask process) as illustrated in fig. 3 by mask.
Then, the corrosion-resisting pattern R1 that obtains as mask, is carried out etching to gate electrode layer 2 ', remove corrosion-resisting pattern R1 then, form gate electrode 2 as illustrated in fig. 4.
Then, as shown in Figure 5, on the glass substrate 1 that is formed with gate electrode 2, form the 1st dielectric film 3, and then form the 1st layer α-Si layer 4 ' and etching barrier film 5 ' thereon successively.
Go up at etching barrier film 5 ' and to form the photoresist tunicle, this photoresist tunicle is carried out the photoetching process of the operation of selectivity exposure, on this tunicle against corrosion, form pattern, form corrosion-resisting pattern R2 (the 2nd photo-mask process) as illustrated in fig. 6 by comprising by mask.
Then, with the corrosion-resisting pattern R2 that obtains as mask, α-Si layer 4 ' to etching barrier film 5 ' and the 1st layer carries out etching, removes corrosion-resisting pattern R2 then, form as shown in Figure 7 form the 1st layer the α-Si layer 4 of pattern and the duplexer of etching barrier film 5.
As shown in Figure 8, form the 2nd layer α-Si layer 6 ' and source-drain electrode formation metal film 7 ' thereon successively.
Then, go up formation photoresist tunicle at this metal film 7 ', by comprising this photoresist tunicle is carried out the photoetching process of the operation of selectivity exposure, on this tunicle against corrosion, form pattern, form corrosion-resisting pattern R3 (the 3rd photo-mask process) as shown in Figure 9 by mask.
Then, the corrosion-resisting pattern R3 that obtains as mask, is carried out etching, removes corrosion-resisting pattern R3 then the α-Si layer 6 ' of metal film 7 ' and the 2nd layer, as shown in figure 10, on etching barrier film 5, form α-Si layer 6 of the 2nd layer and source electrode and the drain electrode 7 that has formed pattern.
Then, as shown in figure 11, on glass substrate 1, form the 2nd dielectric film 8 '.
Then, go up formation photoresist tunicle at the 2nd dielectric film 8 ', by comprising this photoresist tunicle is carried out the photoetching process of the operation of selectivity exposure, on this photoresist tunicle, form pattern, form corrosion-resisting pattern R4 (the 4th photo-mask process) as shown in figure 12 by mask.
Then, the corrosion-resisting pattern R4 that obtains as mask, is carried out etching to the 2nd dielectric film 8 ', remove corrosion-resisting pattern R4 then, as shown in figure 13, form the 2nd dielectric film 8, its pattern is the shape with contact hole.
Then, as shown in figure 14, on glass substrate 1, form nesa coating 9 '.
Then, go up formation photoresist tunicle at this nesa coating 9 ', by comprising this photoresist tunicle is carried out the photoetching process of the operation of selectivity exposure, on this photoresist tunicle, form pattern, form corrosion-resisting pattern R5 (the 5th photo-mask process) as shown in figure 15 by mask.
Then, the corrosion-resisting pattern R5 that obtains as mask, is carried out etching to nesa coating 9 ', remove corrosion-resisting pattern R5 then, form the nesa coating 9 that has formed pattern as illustrated in fig. 16, can obtain tft array substrate thus.
Making in the method for tft array substrate through this operation, carrying out 5 times (the 1st～the 5th photo-mask process) altogether and use photomask to select the photo-mask process that exposes.
But, also strong day by day to the low price requirement of liquid crystal display cells in recent years, require the simplification of manufacturing process, the inhibition of resist consumption etc. for this reason.
Therefore, in order to respond this needs, the someone has proposed the stepped corrosion-resisting pattern that has different-thickness in zones of different by using, the method that the photo-mask process that in the past needed to carry out 2 times is finished with 1 photo-mask process.In the method, stepped corrosion-resisting pattern is carried out by utilizing its thickness difference, without photo-mask process the pattern of the flat shape of this stepped corrosion-resisting pattern being changed after the etching as mask, afterwards this is used as mask once more, carry out etching.
In patent documentation 1～4, record the technology of the number of times that has reduced photo-mask process, in patent documentation 5～6, record the method for corrosion-resisting pattern being carried out ultraviolet treatment with irradiation.
By said method, can reduce the number of times of photo-mask process in theory, so can suppress the consumption of photoresist thus, also can simplify working process, so be expected in the manufacturing of liquid crystal display cells at a low price, be applied.
But, even being applicable to the anticorrosive additive material of the manufacturing of liquid crystal display cells in the past, the desire utilization forms so stepped corrosion-resisting pattern, its elching resistant or thermotolerance are abundant inadequately, are difficult to realize this method.
Specifically, as mentioned above, stepped corrosion-resisting pattern is used as etched mask before its distortion and after the distortion, thus need have high etch resistance, but be difficult to form stepped corrosion-resisting pattern with so high etch resistance.
In addition, cure to handle after sometimes the corrosion-resisting pattern that is used for the liquid crystal display cells manufacturing being implemented and improve thermotolerance, so that can be anti-in etch processes operation or injection (implantation) treatment process, yet be suitable for making the erosion resistant of liquid crystal display cells in the past, though at a low price and have an ISO, but its thermotolerance is relatively poor, thus through after cure and handle the stair-stepping corrosion-resisting pattern in back and can become fluid state, be difficult to keep the different shape of thickness.
Patent documentation 1: the spy opens the 2004-171002 communique
Patent documentation 2: the spy opens the 2002-334830 communique
Patent documentation 3: the spy opens the 2000-133636 communique
Patent documentation 4: the spy opens the 2000-131719 communique
Patent documentation 5: the spy opens flat 9-15851 communique
Patent documentation 6: specially permit communique No. 2552648
Summary of the invention
The present invention In view of the foregoing proposes just, and its purpose is, provides a kind of elching resistant and thermotolerance outstanding and can form the formation method of the corrosion-resisting pattern of stair-stepping corrosion-resisting pattern.
In addition, the present invention also aims to, the formation method of fine pattern of the formation method of having used corrosion-resisting pattern of the present invention and the manufacture method of using the liquid crystal display cells of this method are provided.
In addition, the present invention also aims to, the eurymeric resist composition of the formation method of a kind of formation method that is used for corrosion-resisting pattern of the present invention and fine pattern is provided.
In order to achieve the above object, the formation method of corrosion-resisting pattern of the present invention, it has: the operation that (A) forms the photoresist tunicle on matrix, and (B) make above-mentioned tunicle against corrosion form the operation of the shape of stepped corrosion-resisting pattern with heavy section and thinner wall section through the photo-mask process that comprises selectivity exposure, it is characterized in that, the polystyrene conversion weight-average molecular weight (Mw) that use contains by gel permeation chromatography measurement surpasses 8000 alkali solubility novolac resin, contain naphthoquinones diazido compound, and the positive light anti-etching agent composition of organic solvent, form above-mentioned photoresist tunicle.
In the formation method of corrosion-resisting pattern of the present invention, as above-mentioned matrix, can use member with sandwich construction, in the described sandwich construction, on glass substrate, gate electrode, the 1st dielectric film, the 1st amorphous silica film, etching barrier film, the 2nd amorphous silica film and source-drain electrode formation metal film have been stacked gradually from the glass substrate side.
In addition, the invention provides a kind of eurymeric resist composition, wherein contain (a) polystyrene conversion weight-average molecular weight (Mw) by gel permeation chromatography measurement and surpass 8000 alkali solubility novolac resin, (b) and contain naphthoquinones diazido compound and (d) organic solvent, can be used for formation at the above-mentioned photoresist tunicle of the formation method of corrosion-resisting pattern of the present invention.
The formation method of fine pattern of the present invention has operation as described below, promptly the formation method by corrosion-resisting pattern of the present invention forms and has after the stepped corrosion-resisting pattern of heavy section and thinner wall section, (E) should implement etch processes as mask to above-mentioned matrix by stepped corrosion-resisting pattern, (F) carries out polishing (ashing treatment) to this stepped corrosion-resisting pattern and removes above-mentioned thinner wall section then, (G) after removing above-mentioned thinner wall section, above-mentioned heavy section is implemented etch processes as mask to above-mentioned matrix, then, (H) remove the heavy section of above-mentioned stepped corrosion-resisting pattern.
Perhaps, the formation method of fine pattern of the present invention has operation as described below, promptly, the formation method of corrosion-resisting pattern of the present invention that has the matrix of above-mentioned sandwich construction by use, formation has after the stepped corrosion-resisting pattern of heavy section and thinner wall section, (E ') should stepped corrosion-resisting pattern forms source-drain electrode as mask and uses metal film, the 2nd amorphous silica film, the etching barrier film, and the 1st the amorphous silica film carry out etching, (F) carries out polishing (ashing treatment) to this stepped corrosion-resisting pattern and removes above-mentioned thinner wall section then, (G ') after removing above-mentioned thinner wall section, above-mentioned heavy section is carried out etch processes to above-mentioned source-drain electrode formation with metal film and above-mentioned the 2nd amorphous silica film as mask, above-mentioned etching barrier film is exposed, then, (H) remove the heavy section of above-mentioned stepped corrosion-resisting pattern.
In addition, the invention provides a kind of eurymeric resist composition, wherein contain (a) polystyrene conversion weight-average molecular weight (Mw) by gel permeation chromatography measurement and surpass 8000 alkali solubility novolac resin, (b) and contain naphthoquinones diazido compound and (d) organic solvent, be used in the formation of the above-mentioned photoresist tunicle in the formation method of fine pattern of the present invention.
The manufacture method of liquid crystal display cells of the present invention is included in the operation that forms pattern of pixels on the glass substrate, wherein forms the part of above-mentioned pattern of pixels by the formation method of fine pattern of the present invention.
In addition, in the manufacture method of liquid crystal display cells of the present invention, after the formation method of the fine pattern of the present invention of the matrix that has above-mentioned sandwich construction by use forms fine pattern, have: (I) make operation, (K) that the 2nd dielectric film forms pattern make nesa coating form the operation of pattern by photoetching process forming the operation, (L) that form nesa coating on the 2nd dielectric film of pattern by photoetching process at the operation that the 2nd dielectric film is set on this fine pattern, (J).
Formation method by corrosion-resisting pattern of the present invention, use the alkali solubility novolac resin and use the eurymeric resist composition of Mw in above-mentioned particular range in the eurymeric resist composition that contains naphthoquinones diazido compound, the alkali solubility novolac resin by using, can form the stepped corrosion-resisting pattern that thermotolerance and elching resistant are good and shape stability is outstanding as the photonasty composition as resinous principle.
When adopting the formation method of fine pattern of the present invention, the elching resistant of stepped corrosion-resisting pattern is outstanding, so after should stepped corrosion-resisting pattern matrix being carried out etching as mask, the material of having removed the thinner wall section of this stepped corrosion-resisting pattern by polishing can be used as mask once more, matrix is carried out etching.Therefore, can reduce the number of times that uses photomask on the photoresist tunicle, to form the photo-mask process of pattern.
Its result can suppress the consumption of photoresist, also can cut down the expense of the photomask of relative high price, and then operation also can obtain simplifying.
Eurymeric resist composition of the present invention is, use the composition with high molecular of Mw in above-mentioned particular range in the eurymeric resist composition that contains naphthoquinones diazido compound, the alkali solubility novolac resin as resinous principle use alkali solubility novolac resin and as the photonasty composition, the corrosion-resisting pattern that forms so use the photoresist tunicle that constitutes by said composition to form pattern, its thermotolerance and elching resistant are good, and shape stability is also outstanding.Therefore, this eurymeric resist composition is suitable as the material of photoresist tunicle in the formation method of the formation method of corrosion-resisting pattern of the present invention and fine pattern, that be used to form stepped corrosion-resisting pattern.
According to the manufacture method of liquid crystal display cells of the present invention, can reduce on glass substrate the number of times of the photo-mask process in the operation that forms pattern of pixels, so can suppress photoresist consumption, reduce employed photomask.In addition, also can simplify manufacturing process, so can be applicable to the manufacturing of liquid crystal display cells at a low price.
Description of drawings
Fig. 1 is the sectional view of embodiment of representing the formation method of the formation method of corrosion-resisting pattern of the present invention and fine pattern with process sequence.
Fig. 2 is the sectional view of a part of representing the manufacturing process of tft array substrate in the past.
Fig. 3 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 4 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 5 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 6 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 7 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 8 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Fig. 9 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 10 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 11 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 12 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 13 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 14 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 15 is the sectional view of the part of the manufacturing process of figure expression tft array substrate in the past before connecing.
Figure 16 is the sectional view of the example of expression tft array substrate.
Among the figure: 1-glass substrate, 2-gate electrode, 3-the 1st dielectric film, 4 '-Di, 1 amorphous silica film, 5 '-etching barrier film, 6 '-Di, 2 amorphous silica films, 7 '-source-drain electrode form uses metal film, 10-matrix, the stepped corrosion-resisting pattern of R-, r1-heavy section, r2-thinner wall section.
Embodiment
＜positive light anti-etching agent composition〉[(a) composition]
Alkali solubility novolac resin (a) in the eurymeric resist composition of the present invention, can from usually positive light anti-etching agent composition, can be used as the resin that tunicle forms material, select arbitrarily to use, so long as be modulated into (a) composition integral body pass through polystyrene conversion weight-average molecular weight (only being designated as Mw in this manual) that gel permeation chromatography (also abbreviating GPC as at this instructions) measures above 8000 all can use.
Mw by making (a) composition surpasses 8000, can make it to have after cure the high-fire resistance that can not occur flow phenomenon in the heating when handling etc., the elching resistant of this moment is good simultaneously, especially can realize the stepped corrosion-resisting pattern that anti-dry-etching is outstanding.The value of Mw is big more, can reach high thermotolerance and elching resistant more.(a) the more preferably scope of the Mw of composition is more than 10000.But, when the Mw of (a) composition is excessive, light sensitivity meeting variation against corrosion, (a) higher limit of the Mw of composition is preferably below 80000, more preferably below 50000.
As the object lesson of alkali solubility novolac resin (a), can enumerate the novolac resin that following illustrative phenols and following illustrative aldehydes is reacted and obtain.
As phenols, can be exemplified as phenol; Metacresol, paracresol, cresols classes such as orthoresol, 2, the 3-xylenols, 2, the 5-xylenols, 3, the 5-xylenols, 3, dimethylbenzene phenols such as 4-xylenols, m-ethylphenol, paraethyl phenol, o-ethyl phenol, 2,3, the 5-pseudocuminol, 2,3,5-triethyl phenol, the 4-tert-butyl phenol, the 3-tert-butyl phenol, the 2-tert-butyl phenol, the 2-tert-butyl group-4-methylphenol, the 2-tert-butyl group-alkyl benzene phenols such as 5-methylphenol, p methoxy phenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to propoxyl group phenol, between alkoxy benzene phenols such as propoxyl group phenol, adjacent isopropenyl phenol, to isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-isopropenylbenzene phenols such as 4-isopropenyl phenol, aryl phenol classes such as phenylphenol, 4,4 '-dihydroxybiphenyl, bisphenol-A, resorcinol, quinhydrones, polyhydroxy benzenes phenols such as pyrogallol etc.They can use separately, can also make up more than 2 kinds and use.In the middle of these phenols, preferred especially metacresol, paracresol, 2,3,5-pseudocuminol.
As above-mentioned aldehydes, can be exemplified as formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, acryl aldehyde, crotonaldehyde, hexamethylene aldehyde (cyclohexane aldehyde), furfural, furylacrolein, benzaldehyde, terephthalic aldehyde, phenyl acetaldehyde, α-phenyl propyl aldehyde, beta-phenyl propyl group aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, cinnamic acid etc.They can use separately, can also make up more than 2 kinds and use.In the middle of these aldehydes, from the easy degree that obtains, preferred formaldehyde, if will improve thermotolerance, then special preferred compositions is used hydroxy benzaldehyde class and formaldehyde.
As above-mentioned acidic catalyst, can use hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid etc.
In addition, by controlling 2 ring body content in (a) composition lower, can reduce the amount of gas evolved when heat treated such as curing after the enforcement, can prevent the appearance of contraction (shrink) phenomenon, macropore, crackle etc. of stepped corrosion-resisting pattern, can suppress simultaneously the pollution in the process chamber that the degassing by stepped corrosion-resisting pattern causes, so preferred.
Here, 2 ring bodies among the present invention are meant the condensation product molecule with 2 phenol rings, and 2 ring body content are meant that the detection wavelength by gpc measurement is the ratio that exists on the chromatogram at 280nm place.In this manual, the measuring that contains of 2 ring bodies uses the numerical value that adopts following GPC system and measure.
Device name: SYSTEM 11 (ProductNames, clear and electrician's corporate system) presets post: KF-G (ProductName, the Shodex corporate system) post: KF-802 (ProductName, Shodex corporate system) detecting device: UV41 (ProductName, Shodex corporate system) measures at the 280nm place.
Solvent etc.: tetrahydrofuran is flow through with 1.0ml/ minute flow, under 35 ℃, measure.
(a) 2 ring body content in the composition are preferably below 4.0%.(a) 2 ring body content in the composition are few more, and the amount of gas evolved in the time of just can further reducing heating more can increase manufacturing cost more but 2 ring body content are more little, so (a) lower limit of 2 ring body content in the composition is preferably about 0.1%.(a) the more preferably scope of 2 ring body content in the composition is about 1.0～3.0%.
Mw and 2 ring body content to (a) composition can carry out following adjustment, and promptly by the synthetic reaction of common novolac resin, the condensation product of synthetic phenols and aldehydes is removed low molecular domains by known operations such as fractionation separation then and can be finished adjustment.
Processing such as fractionation for example can be undertaken by being injected into the method that makes its precipitation in the water after will being dissolved in the good solvent by the novolac resin that condensation reaction obtains, wherein, described good solvent is alcohol such as methyl alcohol, ethanol, ketone such as acetone, MEK, or ethylene glycol monoethyl ether acetate, tetrahydrofuran etc.
Perhaps, can be by in synthetic reaction (condensation reaction) process of novolac resin, carrying out the content (spy opens the 2000-13185 communique) that steam distillation reduces by 2 ring bodies.
(a) composition can be made up of a kind of novolac resin, can also be made up of the novolac resin more than 2 kinds.Under situation about forming by the novolac resin more than 2 kinds, can comprise Mw and be no more than the not novolac resin in 4% following scope of 8000 and 2 ring body content, as long as the Mw of whole (a) composition surpasses 8000, if 2 ring body content 4% are with next better.Therefore, use Mw and the mutually different novolac resin more than 2 kinds of 2 ring body content, can adjust the Mw and the 2 ring body content of (a) composition by appropriate combination.
[(b) composition] (b) contains naphthoquinones diazido compound is the photonasty composition.As this (b) composition, for example can use to be used as the composition of liquid crystal display cells manufacturing with the photonasty composition of positive light anti-etching agent composition all the time.
For example, as (b) composition, the preferred use with what following formula (I) was represented contains phenol hydroxyl compound and 1, the esterification reaction product (b1) of 2-naphthoquinones two nitrine sulfoacid compounds and/or contain phenol hydroxyl compound and 1, the esterification reaction product (b2) of 2-naphthoquinones two nitrine sulfoacid compounds with following formula (II) expression.Above-mentioned 1,2-naphthoquinones two nitrine sulfoacid compounds are preferably 1,2-naphthoquinones two nitrine-5-sulfonyl compound.
[changing 1]
[changing 2]
[in the formula, R
1～R
8Represent that independently of each other hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxy or carbon number are 3～6 naphthenic base, R
9～R
11Represent that independently of each other hydrogen atom or carbon number are 1～6 alkyl, Q represents that hydrogen atom, carbon number are 1～6 alkyl and R
9The carbon number of be combined into is 3～6 a naphthenic base or with the residue of following chemical formula (III) expression,
[changing 3]
(in the formula, R
12～R
13Represent that independently of each other hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxy or carbon number are 3～6 naphthenic base, c represents 1～3 integer), a, b represent 1～3 integer, and d represents 0～3 integer, and n represents 0～3 integer].
(b1) the average esterification yield of composition is 50～70%, is preferably 55～65%, when less than 50% the time, film after occurring easily developing reduces, and reduces on this point having problems at residual film ratio, when surpassing 70%, because so the trend that has storage stability to reduce is not preferred.(b2) the average esterification yield of composition is 40～60%, is preferably 45～55%, and when less than 40% the time, the film after occurring easily developing reduces, and residual film ratio reduces easily.When surpassing 60%, light sensitivity has significantly reduced trend.
As (b2) composition, with following formula (IV) expression contain phenol hydroxyl compound and 1, the esterification reaction product (b3) of 2-naphthoquinones two nitrine sulfoacid compounds, outstanding especially aspect the formation ability of high-resolution corrosion-resisting pattern, so preferred.
[changing 4]
In addition, (b) in the composition except above-mentioned photonasty composition, can also use other quinone two nitrine carboxylates, but their use amount is preferably in (b) composition below the 30 quality %, below 25 quality %.
With respect to alkali solubility novolac resin (a) and total amount 100 mass parts that contain phenol hydroxyl compound (c) described later, the use level of (b) composition in the photo-corrosion-resisting agent composition is preferably 15～40 mass parts %, and is further preferred in the scope of 20～30 mass parts.When the content of (b) composition was less than above-mentioned scope, the decline of transfer printing was more, can't form the corrosion-resisting pattern of required form.On the other hand, when than above-mentioned scope for a long time, the residue thing appears in light sensitivity or resolution meeting deterioration in addition easily after development treatment.
As (b) composition, especially preferred (b1), its reason is that price is very low, can modulate the photo-corrosion-resisting agent composition of ISO simultaneously, thermotolerance is also outstanding.
(b) composition can be selected preferred material according to the exposure wavelength that uses in developing procedure in addition.For example in the operation of selecting to expose, when carrying out ghi line (g line, h line and i line) exposure, can preferably use (b1), when carrying out the i line exposing, preferred (b2) composition that uses, perhaps and with (b1) and (b2).
Especially when carrying out the i line exposing, under also with (b1) and situation (b2), preferred (b2) relatively makes the cooperation ratio of (b1) below 50 mass parts.When the use level of (b1) was too much, resolution or light sensitivity might descend morely.
[(c) composition]
In eurymeric resist composition of the present invention, preferably contain molecular weight and be and contain phenol hydroxyl compound (c), the effect of the light sensitivity that can improve thus below 1000.
Particularly in the manufacturing field of liquid crystal display cells, can improve productive capacity and be very important problem, in addition, because the resist consumption is more, so wish that resist composition light sensitivity height and price are low, when (c) composition is somebody's turn to do in use, can realize low relatively price and ISO, so preferred.In addition, when containing (c) composition, in corrosion-resisting pattern, surperficial difficult melting zone can be formed securely,, the uneven generation of development can be suppressed, so preferred by the difference generation of development time so the film reduction of the etchant resist of unexposed portion is less when developing.
When the molecular weight of (c) composition surpasses 1000, almost can not get improving the effect of light sensitivity, so not preferred.As this (c) composition, can suitably use the molecular weight that uses in the positive light anti-etching agent composition of in the past liquid crystal display cells manufacturing usefulness is to contain the phenol hydroxyl compound below 1000, that wherein uses following general formula (II) expression contains the phenol hydroxyl compound, can effectively improve light sensitivity, and thermotolerance is also good, so more preferred.
[changing 5]
[in the formula, R
1～R
8Represent that independently of each other hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxy or carbon number are 3～6 naphthenic base, R
9～R
11Represent that independently of each other hydrogen atom or carbon number are 1～6 alkyl, Q represents that hydrogen atom, carbon number are 1～6 alkyl and R
9The carbon number of be combined into is 3～6 a naphthenic base or with the residue of following chemical formula (III) expression
[changing 6]
(in the formula, R
12～R
13Represent that independently of each other hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxy or carbon number are 3～6 naphthenic base, c represents 1～3 integer), a, b represent 1～3 integer, and d represents 0～3 integer, and n represents 0～3 integer].
Can use wherein any, also two or more kinds may be used.
In this phenolic compounds, with the compound of following formula (V) expression (1-[1 (4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene) and two (2,3,5-trimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, since outstanding aspect ISOization, high residual film ratioization, so preferred especially, particularly use the compound of this formula (V) expression outstanding aspect ISOization, so preferred.
(changing 7)
With respect to alkali solubility novolac resin 100 mass parts as (a) composition, (c) use level of composition is 1～25 mass parts, is preferably the scope of 5～20 weight %.When the content of (c) composition in the resist composition is very few, can't fully obtain the effect of improving of ISOization, high residual film ratioization, served as for a long time, the residue thing appears on the substrate surface after the development easily, and raw materials cost also increases in addition, so not preferred.
[(d) composition]
Photo-corrosion-resisting agent composition of the present invention, composition, preferred (a)～(c) composition and various adding ingredient are dissolved in the organic solvent (d) and use with the form of solution and to be advisable with (a) with (b).
As organic solvent (d), propylene glycol methyl ether acetate (PGMEA) preferably, its reason is aspect coating outstanding, the film thickness uniformity of the tunicle against corrosion on large-size glass substrate is outstanding.
PGMEA most preferably uses with the form of independent solvent, but also can use the solvent outside the PGMEA, can be exemplified as ethyl lactate, gamma-butyrolacton, propylene glycol monobutyl ether etc.
When using ethyl lactate, with respect to PGMEA, with mass ratio 0.1～10 times of amount, preferably in the scope of 1～5 times of amount, cooperate.
In addition, when using gamma-butyrolacton, with respect to PGMEA, with mass ratio 0.01～1 times of amount, preferably in the scope of 0.05～0.5 times of amount, cooperate.
In the present invention, when being formed for forming the tunicle against corrosion of stepped corrosion-resisting pattern, be necessary that making the thickness of this photoresist tunicle is 1.0～3.0 μ m, be preferably formed the thickness of 1.5～2.5 μ especially, for this reason, use these organic solvents that the total amount of above-mentioned (a)～(c) composition in the photo-corrosion-resisting agent composition is adjusted into respect to the gross mass of composition and below 30 quality %, be advisable, be preferably 20～28 quality %, can obtain good coating this moment, so preferred.
[other compositions]
In photo-corrosion-resisting agent composition of the present invention, in the scope of not damaging purpose of the present invention, can further add various adjuvants such as surfactant, preserving stabilizer.Can make it suitably contain the ultraviolet light absorber that for example is used for antihalation, for example 2,2 ', 4,4 '-tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4 '-dihydroxy benaophenonel, 5-amino-3-methyl isophthalic acid-phenyl-4-(4-hydroxy phenyl azo) pyrazoles, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylamino-4 '-ethoxy azobenzene, 4-DEAB, curcumin etc.; Also be useful on the surfactant that prevents streak in addition, for example Off ロ ラ one De FC-430, FC431 (trade name, Sumitomo 3M (strain) system), エ Off ト ッ プ EF122A, EF122B, EF122C, EF126 (trade name, ト one ケ system プ ロ ダ Network ッ (strain) system) etc. fluorine is a surfactant, メ ガ Off ァ ッ Network R-60 (trade name, big Japanese ink chemical industry system) waiting fluoro-silicon is surfactant, BYK-310 (trade name, PVC ッ Network ケ ミ one makes) etc.
Below, be example with the situation that is applied to make liquid crystal display cells, with reference to Fig. 1 to the formation method of corrosion-resisting pattern of the present invention and use the embodiment of formation method of the fine pattern of this method to describe.
At first, prepare matrix.Matrix of the present invention is not particularly limited, but when on using substrate, being laminated with need more than 2 layers and carrying out the matrix of etched layer, can effectively obtains effect of the present invention, so preferred.
When making liquid crystal display cells, as matrix 10, for example shown in Fig. 1 (a), can use the matrix that has multi-ply construction at glass substrate 1, constituting from glass substrate 1 side of described multi-ply construction stacks gradually gate electrode the 2, the 1st dielectric film the 3, the 1st amorphous silica film 4 ', etching barrier film 5 ', the 2nd amorphous silica film 6 ' and the source-drain electrode formation sandwich construction with metal film 7 '.Can be when forming the pattern of gate electrode 2 by carrying out as above-mentioned Fig. 2～step (comprising the 1st photo-mask process) shown in Figure 4.
Size to glass substrate is not particularly limited, and can be 500 * 600mm
2Above substrate also can be 550 * 650mm
2Above large substrate.
For example can use the conductive material of aluminium (Al), chromium (Cr), titanium (Ti) or molybdenum metals such as (Mo) etc. and form as gate electrode 2.
The 2nd dielectric film 3 for example can be by SiN
xForm.
Etching barrier film 5 ' for example can be by SiN
xForm.
Source-drain electrode forms with metal film 7 ', for example can constitute by stacking gradually the stacked film that titanium (Ti) and aluminium (Al) and titanium (Ti) form.
(A) at first, on matrix 10, form photoresist tunicle R '.Be specially the photo-corrosion-resisting agent composition of coating the invention described above on matrix 10, following heat drying (prebake) forms photoresist tunicle R ' thus about 100～140 ℃.
The thickness of photoresist tunicle R ' is preferably about 1.0～3.0 μ m.From obtaining the viewpoint of resist light sensitivity and manufacturing stability simultaneously, the thickness that preferably makes photoresist tunicle R ' is in this scope.
(B) then, through photo-mask process, shown in Fig. 1 (b), make photoresist tunicle R ' form pattern with heavy section r1 and thinner wall section r2.Specifically, the mask (reticule) of having set transmitance by half-tone (halftone) mask etc. carries out the selectivity exposure to photoresist tunicle R ', then develop, wash, form zones of different thus and have difference and stepped corrosion-resisting pattern R thickness, that have heavy section r1 and thinner wall section r2.(the 2nd photo-mask process)
If will only remove thinner wall section r2 and stay the heavy section r1 of suitable depth by polishing afterwards, the difference of heavy section r1 among the stepped corrosion-resisting pattern R and the thickness of thinner wall section r2 is preferably about 0.5～1.5 μ m, and preferred scope is about 0.7～1.3 μ m.
(C) form after the pattern, preferably carry out UV (ultraviolet ray) and solidify (cure) processing.
In the present invention, and nonessential UV curing processing, but, can further improve elching resistant and the thermotolerance of stepped corrosion-resisting pattern R by carrying out this processing.
UV solidifies processing and can use known method to carry out.For example can use the just ultraviolet lamp of the product UMA-802-HC552 by name etc. of motor system of ゥ シ, to whole stepped corrosion-resisting pattern R irradiation ultraviolet radiation.
Elching resistant is outstanding, thermotolerance excellent step shape corrosion-resisting pattern R in order to obtain under the condition that is solidificated in the proterties distortion of avoiding corrosion-resisting pattern by UV, and the ultraviolet irradiation condition optimization is with about 1000～50000mJ/cm
2About exposure irradiation from the ultraviolet ray of the wavelength (about wavelength 200～500nm) of Deep UV zone to visible region.Preferred exposure is 2000～20000mJ/cm
2About.Exposure can be controlled by the ultraviolet intensity and the irradiation time of irradiation.
Wherein, carrying out UV when solidifying (irradiation), for fear of causing gauffer in irradiation portion, preferably the temperature rising that causes to rapid irradiation or because of irradiation is controlled.
(D) in addition, cure processing after preferably stepped corrosion-resisting pattern R being carried out.
When carrying out UV curing processing, cure after after this UV solidifies processing, carrying out.
When carrying out UV curing processing, and cure processing after the nonessential enforcement, but, particularly can improve dry-etching by curing the thermotolerance and the elching resistant that can further improve stepped corrosion-resisting pattern R after carrying out.In addition, by after cure processing, the adhesiveness of stepped corrosion-resisting pattern R and matrix 10 can improve, so even also can obtain height endurability in wet etch process.
In the present invention, the eurymeric resist composition self that is used to form the photoresist tunicle has higher elching resistant, so even with after the temperature conditions that cures in the treatment process be provided with lowlyer, also can effectively improve based on after the elching resistant that cures.
For example, with regard to after cure with regard to the heating condition in the processing, preferably being set as temperature conditions is 100～150 ℃, heating condition is about 1～5 minute.Preferred heating condition is about 110～130 ℃, 1～2 minute.Wherein, particularly, preferably under the temperature conditions below 120 ℃, carry out in order to prevent the change of shape of stepped corrosion-resisting pattern R infalliblely.
Also have, the thermotolerance of eurymeric resist composition self that is used to form the photoresist tunicle is higher, from this point, and the distortion of curing stepped corrosion-resisting pattern R in the treatment process after also can suppressing.In addition,, solidify to handle by UV and can further improve the thermotolerance of stepped corrosion-resisting pattern R when carrying out curing after UV carries out after solidify handling when handling, thus can further suppress infalliblely by after cure the pattern deformation that processing causes.
(E) subsequently, stepped corrosion-resisting pattern R as mask, shown in Fig. 1 (c), is carried out etching to the metal film 7 ' of matrix 10.The etching of metal film 7 ' can adopt known method to carry out.Usually adopt wet etch process, also can adopt dry-etching.
Then, identical stepped corrosion-resisting pattern R as mask, shown in Fig. 1 (d), is carried out etching to the 2nd amorphous silica film 6 ' and etching barrier film 5 ' and the 1st amorphous silica film 4 ' under it that exposes by the etching of described metal film 7 '.The etching of these layers can be undertaken by known method.Normally used is that dry-etching is handled.
Dry-etching is handled and is comprised physical method and chemical method, can use arbitrarily among the present invention, can suitably select according to the material of etched object.
(F) afterwards, stepped corrosion-resisting pattern R is implemented polishing, shown in Fig. 1 (e), remove thinner wall section r2.Polishing can adopt known method to carry out.
When stepped corrosion-resisting pattern R was carried out polishing, film takes place simultaneously for heavy section r1 and thinner wall section r2 reduced, and thinner wall section r2 is removed fully thereupon, exposes the metal film 7 ' under it, becomes the residual state that heavy section r1 is arranged.Under this state, stop polishing, can only remove thinner wall section r2.When remaining heavy section r1 crosses when thin, abundant inadequately as the function of etching mask, so the thickness of residual heavy section r1 is preferably more than the 0.5 μ m.
(G) then, shown in Fig. 1 (f), residual heavy section r1 as mask, to carrying out etch processes by removing the metal film 7 ' that above-mentioned thinner wall section r2 exposes, is formed source electrode and drain electrode 7 thus.
Then, shown in Fig. 1 (g), as mask, the 2nd amorphous silica film 6 ' that the etch processes of the metal film 7 ' by is last time exposed carries out etch processes with residual heavy section r1, forms the 2nd amorphous silica film 6 that has formed pattern thus.
(H) then, remove heavy section r1.The method of removing of heavy section r1 can be undertaken by known method such as polishings.
By above-mentioned operation, can obtain the fine pattern that structure is same as above-mentioned structure shown in Figure 10.
Subsequently, can by with above-mentioned Figure 11～identical operation of operation shown in Figure 15, make tft array substrate.That is, (I) as shown in figure 11, on the fine pattern that the operation by last time obtains, form the 2nd dielectric film 8 '.The 2nd dielectric film 8 ' for example can be by SiN
xForm.
(J) go up the formation photoresist at the 2nd dielectric film 8 ', the photoetching process that this photoresist carries out the operation of selectivity exposure is formed pattern on this tunicle against corrosion, form corrosion-resisting pattern R4 shown in Figure 12 (the 3rd photo-mask process) by comprising by mask.The corrosion-resisting pattern R4 that obtains as mask, is carried out etching to the 2nd dielectric film 8 ', remove corrosion-resisting pattern R4 then, thus, as shown in figure 13, obtain forming the 2nd dielectric film 8 of pattern form with contact hole.
(K) as shown in figure 14, forming formation nesa coating 9 ' on figuratum the 2nd dielectric film 8.Nesa coating 9 ' for example can be formed by ITO (tin indium oxide).
(L) go up formation photoresist tunicle at nesa coating 9 ', by comprising the photoetching process that this photoresist tunicle carries out the operation of selectivity exposure is formed pattern on this tunicle against corrosion, form corrosion-resisting pattern R5 shown in Figure 15 (the 4th photo-mask process) by mask.
Subsequently, the corrosion-resisting pattern R5 that obtains is carried out etching as mask to nesa coating 9 ', remove corrosion-resisting pattern R5 then, form the nesa coating 9 that has formed pattern thus as shown in figure 16, obtain tft array substrate.
In the mode of holding liquid crystal between tft array substrate that so obtains and subtend substrate, assemble by known method and to obtain liquid crystal display cells.
According to present embodiment, can form the high stair-stepping corrosion-resisting pattern R of elching resistant, so should stepped corrosion-resisting pattern R as mask, after metal film 7 ', the 2nd amorphous silica film 6 ', etching barrier film 5 ' and the 1st amorphous silica film 4 ' of matrix 10 carried out etching, can carry out etching to metal film 7 ' and the 2nd amorphous silica film 6 ' with the heavy section r1 of this stepped corrosion-resisting pattern R as mask.
Therefore, can reduce the number of times of the photo-mask process in the manufacturing process of tft array substrate.For example, in the method in the past of Fig. 2～shown in Figure 15, in making tft array substrate, need 5 photo-mask processs (the 1st～the 5th photo-mask process), but in the present embodiment, can make the tft array substrate of same structure by 4 photo-mask processs (the 1st～the 4th photo-mask process).Thus, can suppress the consumption of photoresist, can simplify working process, so can cut down the manufacturing cost of tft array substrate.
In addition, the stepped corrosion-resisting pattern R of Xing Chenging in the present embodiment, its thermotolerance is also good, so cure the distortion in the processing after can preventing.
And then, by implement UV solidify handle and/or after cure processing, can further improve thermotolerance and the elching resistant of stepped corrosion-resisting pattern R.If carry out that UV solidify to handle and after cure and handle these two kinds of processing, can further improve thermotolerance and the elching resistant of stepped corrosion-resisting pattern R.
Also have, in the present embodiment, stepped corrosion-resisting pattern is made as the cross section recess, but the shape of stepped corrosion-resisting pattern is so long as have shape different-thickness, that have heavy section and thinner wall section in zones of different and get final product, and can suitably design according to the shape of the fine pattern that is formed by etching.For example, can be the cross section convex shape that thinner wall section is arranged in the arranged outside of heavy section, can also be cross section chevron shape.
In addition, in the present embodiment, apply the present invention to the operation of α-Si (amorphous silica) shape tft array substrate of structure as shown in figure 16, but be not limited to this example.The present invention can be used to make the base plate of liquid crystal panel with pattern of pixels with various driving elements, is particularly suitable for making the tft array substrate with pattern of pixels of the TFT element that has possessed various structures.The formation method of the fine pattern of the application of the invention forms the part of pattern of pixels, can obtain and this
The effect that embodiment is identical.
[embodiment]
In following embodiment and comparative example, each method of the formation method 1～4 by following corrosion-resisting pattern forms stepped corrosion-resisting pattern, about thermotolerance, anti-dry-etching and moisture-proof formula etching, estimates by method as follows.
(corrosion-resisting pattern formation method 1: no UV solidifies, after cure 120 ℃)
Use the resist-coating device [TR-36000 (chemical industry (strain) system is answered in Tokyo)] that adopts central authorities' dropping and spin-coating method, thickness (50 μ m) with regulation is paved with modulated positive light anti-etching agent composition, then by rotating for 10 seconds with 1000rpm, (360mm * 460mm) goes up and forms resist layer at the glass substrate that is formed with the Ti film.
Then, the temperature of electric hot plate is made as 130 ℃, the vicinity at the interval by about 1mm of being separated by is cured the 1st drying of carrying out for 60 seconds, then the temperature with electric hot plate is made as 120 ℃, the vicinity at the interval by the 0.5mm of being separated by is cured the 2nd drying implementing for 60 seconds, and forming thickness is the photoresist tunicle of 2.0 μ m.
By mask this photoresist tunicle is carried out the selectivity exposure, carry out development treatment, cleaning, the thickness that forms the thickness cross section recess, heavy section shown in Figure 1 and be 2.0 μ m and thinner wall section is that 1.0 μ m, whole width are that the width of 15 μ m, thinner wall section is the shape of the stair-stepping corrosion-resisting pattern of 5 μ m.
Subsequently, carry out 120 ℃, 180 seconds after cure processing, obtain stepped corrosion-resisting pattern.
(corrosion-resisting pattern formation method 2: no UV solidifies, after cure 130 ℃)
In above-mentioned corrosion-resisting pattern formation method 1, except with after cure treatment temperature and change into 130 ℃, adopt identical method to form stepped corrosion-resisting pattern.
(corrosion-resisting pattern formation method 3: have UV to solidify, cure without male offspring)
In above-mentioned corrosion-resisting pattern formation method 1, do not cure processing after after forming pattern, not carrying out, be that 200～500nm, exposure are 3000mJ/cm and replace the enforcement wavelength
2UV solidify (irradiation) processing, in addition, adopt identical method to form stepped corrosion-resisting pattern.
(corrosion-resisting pattern formation method 4: have UV solidify, after cure 120 ℃)
In above-mentioned corrosion-resisting pattern formation method 1, after forming pattern, the enforcement wavelength is that 200～500nm, exposure are 3000mJ/cm
2UV solidify (irradiation) processing, and then carry out 120 ℃, 180 seconds after cure processing, in addition, adopt identical method to form stepped corrosion-resisting pattern.
(1) thermotolerance evaluation:
For the corrosion-resisting pattern that in embodiment and comparative example, obtains, carry out 130 ℃, 300 seconds heat treated, what afterwards the shape of corrosion-resisting pattern is not deformed is designated as zero, deform be designated as *.
(2) anti-dry-etching evaluation:
For the corrosion-resisting pattern that in embodiment and comparative example, obtains, use dry-etching device " TCE-7612X " (the device name: chemical industry system is answered in Tokyo), as etching gas, use CF with 40 milliliters/min, 40 milliliters/min, the amount of 160 milliliters/min respectively
4, CF
3, He, at 300mTorr
-1Reduced pressure atmosphere under, carry out dry-etching with the treatment conditions of 700W-400kHz, 20 ℃ of level temperature (stage temperature), 25 ℃ of target temperature and handle, will the shape of corrosion-resisting pattern not deform before and after handling be designated as zero, distortion is designated as △ a little.
(3) moisture-proof formula etching is estimated:
For the corrosion-resisting pattern that obtains in embodiment and comparative example, the substrate that will be formed with this corrosion-resisting pattern impregnated in the Wet-type etching liquid of setting 20 ℃ for and [contains hydrofluorite (HF)/ammonium fluoride (NH
4F)=1/6 the aqueous solution of the 20 quality % of (mass ratio)] in 10 minutes, carry out wet etch process thus, the corrosion-resisting pattern after the processing is not designated as zero from what underlay substrate was peeled off, and the △ that is designated as that peels off is arranged slightly, peeled off be designated as *.
(embodiment 1)
With method modulation positive light anti-etching agent composition as follows.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=30000 that obtains] 100 mass parts
(b) composition: 2,3,4,1 mole of 4 '-tetrahydroxybenzophenone and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, the modulation positive light anti-etching agent composition.
The positive light anti-etching agent composition that use obtains uses above-mentioned corrosion-resisting pattern formation method 1～4 to form stepped corrosion-resisting pattern respectively.
For each the stepped corrosion-resisting pattern that obtains, its thermotolerance, anti-dry-etching and moisture-proof formula etching have been estimated.Its result is shown in following table 1.
(embodiment 2)
Except the composition with eurymeric resist composition makes into the following composition, be identically formed stepped corrosion-resisting pattern with embodiment 1, and estimate its characteristic.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=30000 that obtains] 100 mass parts
(b) composition: with 1 mole of the phenolic compounds [two (2-methyl-4-hydroxyl-5-cyclohexyl phenyl)-3,4-dihydroxy benzenes methylmethane] of above-mentioned formula (IV) expression and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, the modulation positive light anti-etching agent composition.
(embodiment 3)
Except the composition with positive light anti-etching agent composition makes following composition into, be identically formed stepped corrosion-resisting pattern with embodiment 1, and estimate its characteristic.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=15000 that obtains] 100 mass parts
(b) composition: 2,3,4,1 mole of 4 '-tetrahydroxybenzophenone and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, the modulation positive light anti-etching agent composition.
(comparative example 1)
Except the composition with positive light anti-etching agent composition makes following composition into, be identically formed stepped corrosion-resisting pattern with embodiment 1, and estimate its characteristic.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=8000 that obtains] 100 mass parts
(b) composition: 2,3,4,1 mole of 4 '-tetrahydroxybenzophenone and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, modulation eurymeric resist composition.
(comparative example 2)
Except the composition with positive light anti-etching agent composition makes following composition into, be identically formed stepped corrosion-resisting pattern with embodiment 1, and estimate its characteristic.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=8000 that obtains] 100 mass parts
(b) composition: with 1 mole of the phenolic compounds [two (2-methyl-4-hydroxyl-5-cyclohexyl phenyl)-3,4-dihydroxy benzenes methylmethane] of above-mentioned formula (IV) expression and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, the modulation positive light anti-etching agent composition.
(comparative example 3)
Except the composition with positive light anti-etching agent composition makes following composition into, be identically formed stepped corrosion-resisting pattern with embodiment 1, and estimate its characteristic.
(a) composition: cresols novolac resin [adopting common method to make the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction and the resin of the weight-average molecular weight (Mw)=5000 that obtains] 100 mass parts
(b) composition: 2,3,4,1 mole of 4 '-tetrahydroxybenzophenone and 1, esterification reaction product 27.5 mass parts that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles
(c) composition: 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene 10 mass parts
(d) composition: PGMEA 372.5 mass parts
After uniform dissolution above-mentioned (a)～(d) composition, to wherein cooperating BYK-310 (PVC ッ Network ケ ミ one corporate system) 400ppm as surfactant, the use aperture is that the membrane filter of 0.2 μ m filters it, the modulation positive light anti-etching agent composition.
Table 1
| The formation of corrosion-resisting pattern | Thermotolerance | Anti-dry-etching | Moisture-proof formula etching | |||
| Method | UV solidifies | After cure | ||||
| Embodiment 1 | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | ○ ○ ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
| | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | ○ ○ ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
| | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | ○ ○ ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
| Comparative example 1 | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | × × ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
| Comparative example 2 | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | × × ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
| Comparative example 3 | 1 2 3 4 | Not having has | 120 ℃ 130 ℃ are not had 120 ℃ | × × ○ ○ | △ ○ ○ ○ | ○ ○ × △ |
Claims (13)
1, a kind of formation method of corrosion-resisting pattern, it has: (A) form the operation of photoresist tunicle and (B) make described photoresist tunicle form the operation of the stepped corrosion-resisting pattern shape with heavy section and thinner wall section through the photo-mask process that comprises the selectivity exposure on matrix, it is characterized in that
Use contains (a) polystyrene conversion weight-average molecular weight by gel permeation chromatography measurement and surpasses 8000 alkali solubility novolac resin, (b) and contain the naphthoquinones diazido compound and (d) positive light anti-etching agent composition of organic solvent, forms described photoresist tunicle.
2, the formation method of corrosion-resisting pattern as claimed in claim 1 is characterized in that,
The described polystyrene conversion weight-average molecular weight of described alkali solubility novolac resin is more than 10000.
3, the formation method of corrosion-resisting pattern as claimed in claim 1 is characterized in that,
Make after the photoresist tunicle forms the operation of pattern at described (B), have the operation of curing processing after (D) carries out.
4, the formation method of corrosion-resisting pattern as claimed in claim 3 is characterized in that,
The temperature conditions that cures in the processing after described (D) is made as below 120 ℃.
5, the formation method of corrosion-resisting pattern as claimed in claim 3 is characterized in that,
At described (B) the photoresist tunicle is formed and cure between the operation of processing after the operation of pattern and described (D) carry out, have (C) and carry out UV and solidify the operation of handling.
6, the formation method of corrosion-resisting pattern as claimed in claim 1 is characterized in that,
As described matrix, use to have on glass substrate to stack gradually the material that gate electrode, the 1st dielectric film, the 1st amorphous silica film, etching barrier film, the 2nd amorphous silica film and source-drain electrode form the sandwich construction of using metal film from the glass substrate side.
7, a kind of positive light anti-etching agent composition, it is characterized in that, be used to form the described photoresist tunicle in the formation method of the described corrosion-resisting pattern of claim 1, contain (a) polystyrene conversion weight-average molecular weight by gel permeation chromatography measurement and surpass 8000 alkali solubility novolac resin, (b) and contain naphthoquinones diazido compound and (d) organic solvent.
8, a kind of formation method of fine pattern is characterized in that, has operation as described below:
Form by the described method of claim 1 and to have after the stepped corrosion-resisting pattern of heavy section and thinner wall section, (E) should implement etch processes as mask to described matrix by stepped corrosion-resisting pattern, (F) carries out polishing to this stepped corrosion-resisting pattern then, remove described thinner wall section, (G) after removing described thinner wall section, described heavy section is implemented etch processes as mask to described matrix, then, (H) remove the heavy section of described stepped corrosion-resisting pattern.
9, a kind of formation method of fine pattern is characterized in that, has operation as described below:
Form by the described method of claim 6 and to have after the stepped corrosion-resisting pattern of heavy section and thinner wall section, (E ') should stepped corrosion-resisting pattern forms described source-drain electrode as mask and uses metal film, described the 2nd amorphous silica film, described etching barrier film, and described the 1st amorphous silica film carries out etch processes, (F) carries out polishing to described stepped corrosion-resisting pattern then, remove described thinner wall section, (G ') after removing described thinner wall section, described heavy section is carried out etch processes to described source-drain electrode formation with metal film and described the 2nd amorphous silica film as mask, described etching barrier film is exposed, then, (H) remove the heavy section of described stepped corrosion-resisting pattern.
10, the formation method of fine pattern as claimed in claim 9 is characterized in that,
The etch processes that described source-drain electrode forms with metal film is that wet etch process or dry-etching are handled, and the etch processes of described the 2nd amorphous silica film is that dry-etching is handled.
11, a kind of positive light anti-etching agent composition, it is characterized in that, be used to form the described photoresist tunicle in the formation method of any described fine pattern in the claim 8～10, contain (a) polystyrene conversion weight-average molecular weight by gel permeation chromatography measurement and surpass 8000 alkali solubility novolac resin, (b) and contain naphthoquinones diazido compound and (d) organic solvent.
12, a kind of manufacture method of liquid crystal display cells is the manufacture method with liquid crystal display cells of the operation that forms pattern of pixels on glass substrate, it is characterized in that,
Form the part of described pattern of pixels by the formation method of the described fine pattern of claim 8.
13, a kind of manufacture method of liquid crystal display cells, it is characterized in that, after described method forms fine pattern by claim 9, have: (I) operation, (K) that makes the 2nd dielectric film form pattern by photoetching process at the operation that the 2nd dielectric film is set on this fine pattern, (J) makes nesa coating form the operation of pattern at the operation, (L) that form formation nesa coating on the 2nd dielectric film of pattern by photoetching process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004256746A JP4611690B2 (en) | 2004-09-03 | 2004-09-03 | Method for forming resist pattern, method for forming fine pattern using the same, and method for manufacturing liquid crystal display element |
| JP2004256746 | 2004-09-03 |
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| Publication Number | Publication Date |
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| CN1743954A true CN1743954A (en) | 2006-03-08 |
| CN100545750C CN100545750C (en) | 2009-09-30 |
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| CNB2005100845386A Active CN100545750C (en) | 2004-09-03 | 2005-07-26 | The formation method of corrosion-resisting pattern and use the formation method of fine pattern of this method and the manufacture method of liquid crystal display cells |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4611690B2 (en) |
| KR (1) | KR100758865B1 (en) |
| CN (1) | CN100545750C (en) |
| TW (1) | TWI312442B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6443435A (en) * | 1987-08-11 | 1989-02-15 | Minolta Camera Kk | Paper skew detecting device |
| KR101430962B1 (en) * | 2008-03-04 | 2014-08-18 | 주식회사 동진쎄미켐 | Photoresist composition and method of manufacturing array substrate using the same |
| JP5189909B2 (en) * | 2008-07-04 | 2013-04-24 | 東京応化工業株式会社 | Positive resist composition for lift-off |
| JP6302643B2 (en) * | 2013-11-08 | 2018-03-28 | 東京応化工業株式会社 | Positive resist composition, resist pattern forming method, pattern forming method comprising metal layer, and through electrode manufacturing method |
| WO2016072024A1 (en) * | 2014-11-07 | 2016-05-12 | 堺ディスプレイプロダクト株式会社 | Method for manufacturing thin-film transistor, thin-film transistor, and display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6057339A (en) * | 1983-09-08 | 1985-04-03 | Sumitomo Chem Co Ltd | Positive type photoresist composition |
| JPS61275748A (en) * | 1985-05-29 | 1986-12-05 | Sumitomo Chem Co Ltd | Positive type photoresist composition |
| JPS6214148A (en) * | 1985-07-11 | 1987-01-22 | Sumitomo Chem Co Ltd | Positive type photoresist composition |
| JPS6411259A (en) * | 1987-07-03 | 1989-01-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
| JPH0540336A (en) * | 1991-08-07 | 1993-02-19 | Hitachi Chem Co Ltd | Photosensitive resin composition |
| JP3302475B2 (en) * | 1993-12-27 | 2002-07-15 | カシオ計算機株式会社 | Method for manufacturing thin film transistor array |
| JP3453615B2 (en) * | 2000-04-14 | 2003-10-06 | 光陽化学工業株式会社 | Positive photoresist composition |
| JP2002098996A (en) * | 2000-09-25 | 2002-04-05 | Sharp Corp | Method of manufacturing matrix substrate for liquid crystal |
| JP4339005B2 (en) * | 2002-04-04 | 2009-10-07 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
| KR100493383B1 (en) * | 2002-10-01 | 2005-06-07 | 엘지.필립스 엘시디 주식회사 | method for forming metal pattern of liquid crystal display device |
| JP2004177683A (en) * | 2002-11-27 | 2004-06-24 | Clariant (Japan) Kk | Method for forming pattern by using ultrahigh heat-resistant positive photosensitive composition |
| JP4345348B2 (en) * | 2003-05-09 | 2009-10-14 | Ｊｓｒ株式会社 | Method for forming protrusion for vertical alignment type liquid crystal display element and spacer for vertical alignment type liquid crystal display element |
| JP4232527B2 (en) * | 2003-05-09 | 2009-03-04 | Ｊｓｒ株式会社 | Method for forming protrusion for vertical alignment type liquid crystal display element and spacer for vertical alignment type liquid crystal display element |
| JP4275519B2 (en) * | 2003-12-12 | 2009-06-10 | 東京応化工業株式会社 | Method for forming fine pattern and method for manufacturing liquid crystal display element |
| JP2006003422A (en) * | 2004-06-15 | 2006-01-05 | Fuji Photo Film Co Ltd | Method for forming pattern, and tft array substrate, and liquid crystal display element |
-
2004
- 2004-09-03 JP JP2004256746A patent/JP4611690B2/en not_active Expired - Fee Related
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- 2005-07-01 TW TW094122387A patent/TWI312442B/en active
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| TW200609677A (en) | 2006-03-16 |
| TWI312442B (en) | 2009-07-21 |
| CN100545750C (en) | 2009-09-30 |
| KR20060053968A (en) | 2006-05-22 |
| JP4611690B2 (en) | 2011-01-12 |
| JP2006072080A (en) | 2006-03-16 |
| KR100758865B1 (en) | 2007-09-14 |
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